RAW LAW
The experimental expression of rate of reaction in terms of concentration
of reactants is known as rate law or rate expression.
The relationship between rate of reaction and concentration of reactants
is a complex one and it is determined experimentally.
In this expression the rate of a reaction is proportional to the product of
molar concentration of reactants with each term raised to the power or
exponent that has to be found experimentally.
In a chemical reaction : aA + bB ⎯→ Product A
Rate µ [A]x[B]y
A+B→C
A B
C
If concentration of B is Doubled
A+B→C
A B
Rate of reaction doesn’t change.
r∝ 𝐁 𝟎
CC
If concentration of A is Doubled
A+B→C
A B
Rate of reaction becomes doubled.
r∝ 𝐀 𝟏
C
RAW LAW
In a chemical reaction : aA + bB ⎯→ Product
Rate µ [A]x[B]y
The values of exponents x and y are found experimentally which may or
may not be same as stoichiometric coefficients.
Rate = k[A]x[B]y
where k is a proportionality constant known as rate constant or specific
reaction rate.
RATE CONSTANT
Rate = k[A]x[B]y
If [A] = [B] = 1M
then, r = k
Rate of reaction at unit concentration of each reactant involved in the
reaction is known as rate constant.
Rate constant does not depend on concentration of reactant but it
depends on temperature and catalyst.
Some important point
Law of mass action (LOMA) is a special case of rate law where exponents
are equal to stoichiometric coefficient.
In a chemical reaction : aA + bB ⎯→ Product
Rate = k[A]x[B]y
According to Rate Law,
According to Law of mass action (LOMA),
Rate µ [A]a[B]b
LOMA is a theoretical concept while rate law is an experimental concept.
The sum of powers of concentration of reactants in rate law expression is
known as order of reaction.
For the reaction, aA + bB → Product
Rate law : Rate = k[A]x[B]y
Here x = order of reaction with respect to A
y = order of reaction with respect to B
x + y = n (overall order of reaction)
Order of reaction is an experimental quantity.
Order of reaction may be zero, positive, negative or fractional.
It shows dependency of ROR on concentration of reactant.
EXAMPLE
For a reaction 2A + B → Product ; its rate law r = k[A]x [B]y
(i) If [A] is doubled, ROR becomes doubled then value of x is ?
(ii) If [A] is increased by four times, ROR becomes doubled then
value of x is?
(iii) If [B] is doubled, ROR becomes halved then value of y is?
(iv) If [B] is doubled, ROR shows no change then value of y is?
SOLUTION
EXAMPLE
For a reaction 2A + B → Product ; its rate law r = k[A]x [B]y
(i) If [A] is doubled, ROR becomes doubled then value of x is ?
(ii) If [A] is increased by four times, ROR becomes doubled then
value of x is?
(iii) If [B] is doubled, ROR becomes halved then value of y is?
(iv) If [B] is doubled, ROR shows no change then value of y is?
SOLUTION
EXAMPLE
For a reaction 2A + B → Product ; its rate law r = k[A]x [B]y
(i) If [A] is doubled, ROR becomes doubled then value of x is ?
(ii) If [A] is increased by four times, ROR becomes doubled then
value of x is?
(iii) If [B] is doubled, ROR becomes halved then value of y is?
(iv) If [B] is doubled, ROR shows no change then value of y is?
SOLUTION
EXAMPLE
For a reaction 2A + B → Product ; its rate law r = k[A]x [B]y
(i) If [A] is doubled, ROR becomes doubled then value of x is ?
(ii) If [A] is increased by four times, ROR becomes doubled then
value of x is?
(iii) If [B] is doubled, ROR becomes halved then value of y is?
(iv) If [B] is doubled, ROR shows no change then value of y is?
SOLUTION
Unit of rate constant
A ⎯→ Product ; Rate = k[A]n
mol –1
r unit of rate × time
k= = = L
An unit of concentration n mol n
L
1–n
mol
Unit of k = × time–1 = (M)1–n × time–1
L
For gaseous reaction unit of k may be = (atm)1–n × time–1
Unit of k = (mol L–1 )1–n × time–1 = (M)1–n × time–1
(i) If n = 0 (zero order reaction)
k = (mol L–1)1–0 time–1 = mol L–1 time–1
(ii) If n = 1 (first order reaction)
k = (mol L–1)1–1 time–1 = time–1
(iii) If n = 2 (second order reaction)
k = (mol L–1)1–2 time–1 = mol–1 L time–1
EXAMPLE
Rate law of a gaseous reaction :- A(g) + 2B(g) → C(g) is r = k[A][B]2, Find
the effect on rate of reaction, if :-
(i) Concentration of both A & B are tripled.
(ii) Pressure of only B is halved.
(iii) Volume of container is reduced to 1/4th of the initial volume.
SOLUTION
SOLUTION
EXAMPLE
For mA + nB → P, the concentration of both reactants is doubled then the
rate of reaction is increased 8 times and if only concentration of B is
doubled rate of reaction is doubled. Calculate order of reaction and rate
law equation.
SOLUTION
SOLUTION
EXAMPLE
For A + B → P ; When concentration of A is doubled the rate become 2.82
times, when concentration of B is tripled the rate is also tripled then
determine rate law equation?
SOLUTION
SOLUTION
EXAMPLE
For a reaction rate law equation is r = k(C)3/2. Then unit of rate constant
will be.
SOLUTION
EXAMPLE
Find out order of this reaction : A + B → Product
[A] [B] ROR
(1) 0.05 M 0.05 M 1.2 × 10–3
(2) 0.10 M 0.05 M 2.4 × 10–3
(3) 0.05 M 0.1 M 1.2 × 10–3
SOLUTION
SOLUTION
EXAMPLE
Find out rate constant for the reaction A2 + B2 → 2AB
[A2] [B2] (ROA)AB
0.1 M 0.1 M 2.5 × 10–4
0.2 M 0.1 M 5 × 10–4
0.2 M 0.2 M 10 × 10–4
SOLUTION